JP2018204034A - Polyimide film - Google Patents

Abstract

To provide a polyimide film that has excellent transparency and heat resistance, also has a low linear thermal expansion coefficient, and can be suitably used for e.g. substrates for displays, touch panels, or solar cells.SOLUTION: A polyimide film has a film thickness of 10 μm, has a weight retention rate of 99.0% or more when held for 4 hours at 400°C, a YI (yellowness) of 10 or less, and a linear thermal expansion coefficient between 100-350°C of 55 ppm/K or less.SELECTED DRAWING: None

Description

  The present invention relates to a polyimide film and a substrate for a display, a touch panel, or a solar cell.

  In recent years, with the arrival of an advanced information society, development of optical materials such as a liquid crystal alignment film and a protective film for a color filter in the display device field, such as an optical fiber and an optical waveguide in the optical communication field, is progressing. In particular, in the field of display devices, a plastic substrate that is lightweight and excellent in flexibility as a substitute for a glass substrate has been studied, and a display that can be bent and rolled has been actively developed. For this reason, there is a demand for higher performance optical materials that can be used for such applications.

  Many polyimide films have been proposed as plastic substrates instead of glass substrates (for example, Patent Documents 1 to 3). However, various characteristics are required for the substrate of the display device, and further improvement of the proposed polyimide film has been desired.

  In addition to the substrate, a plastic cover sheet (protective film) has been studied as an alternative to the cover glass for protecting the display surface. However, the conventional polyimide film has room for further improvement as a cover sheet (protective film) for the display surface.

International Publication No. 2013/069725 Special table 2010-538103 gazette JP 2017-82225 A

  The present invention is a polyimide film that can be suitably used for various applications such as a display, a touch panel, or a solar cell substrate. Specifically, the polyimide film is excellent in transparency and heat resistance, and has a linear thermal expansion coefficient. The object is to provide a low polyimide film.

The present invention relates to the following items.
1. A film containing polyimide,
When the film thickness is measured at 10 μm,
The weight retention when held at 400 ° C. for 4 hours is 99.0% or more,
YI (yellowness) is 10 or less, and
The polyimide film characterized by the linear thermal expansion coefficient between 100-350 degreeC being 55 ppm / K or less.
2. Item 2. The polyimide film according to Item 1, wherein the weight retention when held at 430 ° C. for 1 hour when the film thickness is 10 μm is 99.0% or more.
3. Item 3. The polyimide film according to Item 1 or 2, wherein a linear thermal expansion coefficient between 100 and 380 ° C. when measured at 10 μm is 65 ppm / K or less.
4). Item 4. The polyimide film according to any one of Items 1 to 3, wherein the haze is 2% or less when the film thickness is 10 μm.
5. Item 5. The polyimide film according to any one of Items 1 to 4, wherein a thickness direction retardation (Rth) is 1000 nm or less when the film thickness is measured at 10 μm.
6). Item 6. The polyimide film according to any one of Items 1 to 5, wherein the light transmittance at a wavelength of 308 nm when measured at a film thickness of 10 μm is 0.1% or less.
7). A laminate comprising the polyimide film according to any one of Items 1 to 6 formed on a glass substrate.
8). A substrate for a display, a touch panel, or a solar cell, comprising the polyimide film according to any one of Items 1 to 6.

  According to the present invention, a polyimide film having excellent transparency and heat resistance and a low coefficient of linear thermal expansion can be provided, and in particular, a polyimide that can be suitably used for a substrate for a display, a touch panel, or a solar cell. A film can be provided.

  The polyimide film of the present invention can be suitably used for various applications other than the substrate. For example, it can be suitably used as a cover sheet for protecting the display surface.

It is a figure (TGA chart) which shows the measurement result of the weight retention when hold | maintaining at 400 degreeC for 4 hours of the polyimide film of Example 2. FIG.

  The polyimide film of the present invention is a film containing polyimide. Here, the polyimide means a polymer containing a repeating unit having an imide structure, and includes, for example, polyamideimide, polyetherimide, polyesterimide and the like.

  The polyimide film of the present invention has a weight retention of 99.0% or more, preferably 99.1% or more, more preferably 99, when held at 400 ° C. for 4 hours when measured at a film thickness of 10 μm. .2% or more, particularly preferably 99.3% or more. Furthermore, when the film thickness is measured at 10 μm, it is preferable that the weight retention when held at 430 ° C. for 1 hour is 99.0% or more. When a polyimide film is used for a display substrate or the like, a conductive layer is formed on the surface of the polyimide film to form a transistor. When the film thickness was measured at 10 μm and the weight retention when held at 400 ° C. for 4 hours was 99.0% or more, particularly preferably 99.3% or more, the film thickness was measured at 10 μm. If the weight retention after holding at 430 ° C. for 1 hour in the case is 99.0% or more, a thin film transistor with good characteristics can be obtained withstanding the high temperature manufacturing process. Moreover, contamination of the manufacturing equipment due to the decomposition of the polyimide can be prevented. In order to cope with a wide range of manufacturing processes and to manufacture a thin film transistor having better characteristics while preventing contamination of manufacturing equipment, when the film thickness is measured at 10 μm, when held at 400 ° C. for 4 hours. It may be particularly desired that the weight retention is 99.3% or higher.

  In the present invention, the weight retention rate when kept at 400 ° C. for 4 hours and the weight retention rate when kept at 430 ° C. for 1 hour are values measured under the condition that the sample weight (total weight) is 4 mg. A change in weight may be measured by heating at 400 ° C. for 4 hours or at 430 ° C. for 1 hour in a state where a plurality of polyimide films having a film thickness of 10 μm are stacked.

  The weight retention after holding at 400 ° C. for 4 hours and the weight retention after holding at 430 ° C. for 1 hour tend to decrease as the film thickness decreases.

  The polyimide film of the present invention has a YI (yellowness) measured at a film thickness of 10 μm of 10 or less, preferably 9 or less, more preferably 8 or less, more preferably 7 or less, more preferably 6 or less. Particularly preferably, it is 5 or less. When the polyimide film is used for a light transmitting application such as a display substrate, the polyimide film is required to have transparency. If YI when measured at a film thickness of 10 μm is 10 or less, particularly preferably 5 or less, usually required transparency can be secured. YI tends to increase as the film thickness increases.

  In terms of transparency, the polyimide film of the present invention has a light transmittance at a wavelength of 400 nm when measured at a film thickness of 10 μm, preferably 70% or more, more preferably 72% or more, more preferably 74% or more, Particularly preferably, it is preferably 75% or more. The polyimide film of the present invention has a total light transmittance (average light transmittance of a wavelength of 380 nm to 780 nm) when measured at a film thickness of 10 μm, preferably 70% or more, more preferably 75% or more, and more preferably Is preferably 80% or more, more preferably 82% or more, and particularly preferably 84% or more. Note that the light transmittance at a wavelength of 400 nm and the total light transmittance also tend to decrease as the film thickness increases.

  The polyimide film of the present invention has a linear thermal expansion coefficient between 100 and 350 ° C. of 55 ppm / K or less, preferably 50 ppm / K or less, particularly preferably 45 ppm / K or less when the film thickness is measured at 10 μm. It is. In one embodiment, it is preferable that the coefficient of linear thermal expansion between 100 and 350 ° C. when measured at a film thickness of 10 μm is further lower, more preferably 40 ppm / K or less, more preferably 35 ppm / K or less, Especially preferably, it is 30 ppm / K or less, or less than 30 ppm / K. When a polyimide film is used for a display substrate or the like, a conductive layer is formed on the surface of the polyimide film to form a transistor. If the linear thermal expansion coefficient of the polyimide film is large in the temperature range in the manufacturing process, the difference in the linear thermal expansion coefficient with a conductor such as a metal becomes large, which may cause problems such as increased warpage of the substrate. . In order to obtain a thin film transistor having good characteristics without problems in a normal manufacturing process, at least the linear thermal expansion coefficient between 100 and 350 ° C. when measured at a film thickness of 10 μm is 55 ppm / K or less, particularly preferable. Needs to be 40 ppm / K or less.

  Moreover, in order to cope with a wider manufacturing process, it is preferable that the linear thermal expansion coefficient of the polyimide film is low up to a higher temperature. Specifically, when the film thickness is 10 μm, it is 100 to 380 ° C., more preferably 100 to 390 ° C., more preferably 100 to 400 ° C., more preferably 100 to 410 ° C., and particularly preferably 100 to 420 ° C. The linear thermal expansion coefficient between 0 ° C. is preferably 65 ppm / K or less, more preferably 60 ppm / K or less, more preferably 55 ppm / K or less, more preferably 50 ppm / K or less, and particularly preferably 45 ppm / K or less. It is preferable. In an embodiment, the film thickness is 100 to 380 ° C., more preferably 100 to 390 ° C., more preferably 100 to 400 ° C., more preferably 100 to 410 ° C., and more preferably 100 to 100 ° C., when measured at a film thickness of 10 μm. The linear thermal expansion coefficient between 420 ° C. is preferably 40 ppm / K or less, more preferably 35 ppm / K or less, particularly preferably 30 ppm / K or less, or less than 30 ppm / K.

  Moreover, in a certain embodiment, it is preferable that the linear thermal expansion coefficient between 100-430 degreeC when a film thickness is measured at 10 micrometers is 65 ppm / K or less. Furthermore, when the film thickness is measured at 10 μm, the linear thermal expansion coefficient between 100 and 430 ° C. is preferably 60 ppm / K or less, more preferably 55 ppm / K or less.

  The linear thermal expansion coefficient in the present invention is measured for a polyimide film having a film thickness of 10 μm under the conditions of a film width of 4 mm, a distance between chucks of 15 mm, a tensile load of 2 g, and a heating rate of 20 ° C./min. It is the value. Here, the linear thermal expansion coefficient tends to decrease as the film thickness increases.

  The polyimide film of the present invention has a haze of preferably 2% or less, more preferably 1.5% or less when measured at a film thickness of 10 μm. When a polyimide film is used for display or the like, if the haze is high, light may be scattered and the image may be blurred. If the haze when measured at a film thickness of 10 μm is 2% or less, such a problem can usually be prevented. Note that the haze tends to increase as the film thickness increases.

  The polyimide film of the present invention preferably has a thickness direction retardation (Rth) of 1000 nm or less, more preferably 850 nm or less, more preferably 830 nm or less when the film thickness is measured at 10 μm. When a polyimide film is used for a display application or the like, if the retardation in the thickness direction is large, there may be a problem that the color of transmitted light is not displayed correctly, the color blurs or the viewing angle becomes narrow. The thickness direction retardation (Rth) tends to increase as the film thickness increases.

  Furthermore, the polyimide film of the present invention preferably has a light transmittance at a wavelength of 308 nm when measured at a film thickness of 10 μm, preferably 0.1% or less, more preferably 0.05% or less. When a polyimide film is used for a substrate or the like, in many manufacturing processes, a polyimide precursor varnish (a composition containing a polyimide precursor) or a polyimide varnish (a composition containing a polyimide) is flowed onto a substrate such as glass. After obtaining a polyimide / base material laminate by heating and heating, laser light (wavelength 308 nm) is irradiated from the base material (glass) surface to peel the polyimide film from the base material. The polyimide film has a high light transmittance at a wavelength of 308 nm, and the polyimide film cannot be peeled off from the substrate unless it absorbs the energy of light (laser light) at a wavelength of 308 nm. In order to apply to a process including a step of peeling a polyimide film from a substrate with a laser, the light transmittance at a wavelength of 308 nm when the film thickness is measured at 10 μm is low, preferably 0.1% or less. is necessary. Note that the light transmittance at a wavelength of 308 nm tends to decrease as the film thickness increases.

  By satisfying the physical property values as described above, a polyimide film that can be suitably used particularly for a substrate for a display, and further a polyimide film that can be suitably used for a substrate for a touch panel, a substrate for a solar cell, etc. can get.

  The details of the method for measuring the physical property values will be described in the examples described later.

  The polyimide film of the present invention is not limited to those having a thickness of 10 μm. The thickness of the polyimide film is appropriately selected depending on the application, and is usually 1 to 250 μm, more preferably 1 to 150 μm, more preferably 1 to 50 μm, and particularly preferably 1 to 30 μm.

  The polyimide film of the present invention can be prepared by using a filler (inorganic or organic particles such as silica), an antioxidant, an ultraviolet absorber, a dye, a pigment, a silane coupling agent, a primer, or a flame retardant, as necessary. It can contain various additives generally used for materials, leveling agents, release agents, and other polyimide films.

  In an embodiment, the polyimide film of the present invention contains inorganic particles such as silica and organic particles (fillers) from the viewpoint of film strength and film surface smoothness, or from the viewpoint of ease of production and cost. Preferably not.

  In the polyimide film of the present invention, for example, one or more repeating units represented by the following chemical formula (1-1) are 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol, based on all repeating units. % Or more of polyimide.

（式中、Ａ_１は、下記化学式（Ａ−１）で表される４価の基であり、Ｂ_１は、下記化学式（Ｂ−１）で表される２価の基である。）

(In the formula, A ₁ is a tetravalent group represented by the following chemical formula (A-1), and B ₁ is a divalent group represented by the following chemical formula (B-1).)

（式中、Ｒ_１、Ｒ_２、Ｒ_３は、それぞれ独立に、−ＣＨ_２−、または−ＣＨ_２ＣＨ_２−である。）

_{(Wherein, R 1, R 2, R} 3 are each independently, -CH ₂ -, or _-CH 2 CH ₂ - in which.)

（式中、ｎ_１は０〜３の整数を示し、ｎ_２は０〜３の整数を示す。Ｙ_１、Ｙ_２、Ｙ_３は、それぞれ独立に、水素原子、メチル基、トリフルオロメチル基よりなる群から選択される１種を示し、Ｑ_１、Ｑ_２は、それぞれ独立に、直接結合、または 式：−ＮＨＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−で表される基よりなる群から選択される１種を示す。）

(In the formula, n ₁ represents an integer of 0 to 3, n ₂ represents an integer of 0 to _3. Y ₁ , Y ₂ , and Y ₃ are each independently a hydrogen atom, a methyl group, or a trifluoromethyl group. Q ₁ and Q ₂ are each independently a direct bond or a group represented by the formula: —NHCO—, —CONH—, —COO—, —OCO—. 1 type selected from the group consisting of:

  In the polyimide film of the present invention, for example, one or more repeating units represented by the following chemical formula (1-2) are 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol, based on all repeating units. % Of polyimide or more.

（式中、Ａ_２は、下記化学式（Ａ−２）で表される４価の基であり、Ｂ_２は、下記化学式（Ｂ−１）で表される２価の基である。）

(In the formula, A ₂ is a tetravalent group represented by the following chemical formula (A-2), and B ₂ is a divalent group represented by the following chemical formula (B-1).)

（式中、ｎ_１は０〜３の整数を示し、ｎ_２は０〜３の整数を示す。Ｙ_１、Ｙ_２、Ｙ_３は、それぞれ独立に、水素原子、メチル基、トリフルオロメチル基よりなる群から選択される１種を示し、Ｑ_１、Ｑ_２は、それぞれ独立に、直接結合、または 式：−ＮＨＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−で表される基よりなる群から選択される１種を示す。）

(In the formula, n ₁ represents an integer of 0 to 3, n ₂ represents an integer of 0 to _3. Y ₁ , Y ₂ , and Y ₃ are each independently a hydrogen atom, a methyl group, or a trifluoromethyl group. Q ₁ and Q ₂ are each independently a direct bond or a group represented by the formula: —NHCO—, —CONH—, —COO—, —OCO—. 1 type selected from the group consisting of:

In the group represented by the chemical formula (B-1), the connection position of the aromatic rings is not particularly limited, but the amide group (—CONH—) bonded to A ₁ or A ₂ or the connection group of the aromatic rings. It is preferable to bond at the 4-position. By bonding in this way, the resulting polyimide has a linear structure and may have low linear thermal expansion. When the group represented by the chemical formula (B-1) has one aromatic ring (when n ₁ and n ₂ are 0), the group represented by the chemical formula (B-1) is a substituent ( It is preferably a p-phenylene group optionally having Y ₁ ). In addition, a methyl group or a trifluoromethyl group may be substituted on the aromatic ring, but the substitution position is not particularly limited.

  Examples of the divalent group represented by the chemical formula (B-1) include groups represented by any of the following chemical formulas (B-1-1) to (B-1-6).

  Moreover, the polyimide film of the present invention has, for example, one or more repeating units represented by the chemical formula (1-1) or (1-2), for example, 60 mol% or more, preferably with respect to all repeating units. A tetravalent group containing 65 mol% or more, more preferably 70 mol% or more, alternatively 75 mol% or more, alternatively 80 mol% or more, alternatively 90 mol% or more and derived from a tetracarboxylic acid component is represented by the chemical formula (A-1 ) Or (A-2), the divalent group derived from the diamine component has a plurality of aromatic rings, and the aromatic rings are connected by an ether bond (—O—). 1 type or more of the repeating unit is, for example, 40 mol% or less, preferably 35 mol% or less, more preferably 30 mol% or less, or 25 mol% or less, or 2 with respect to all repeating units. Mol% or less, or may be made of polyimide comprising 10 mol% or less. In this case, the polyimide is usually a tetravalent group in which the tetravalent group derived from the tetracarboxylic acid component is represented by the chemical formula (A-1) or (A-2), and 2 derived from the diamine component. It is preferable that 5 mol% or more of the repeating unit in which the valent group has a plurality of aromatic rings and the aromatic rings are connected by an ether bond (—O—) with respect to all the repeating units. .

  Examples of the divalent group having a plurality of aromatic rings and part or all of the aromatic rings connected by an ether bond (—O—) include the following chemical formulas (B-2-1) to (B-2). -4) is mentioned.

  However, the polyimide film of the present invention is not limited to those composed of these polyimides.

  Examples of the tetracarboxylic acid component that can be suitably used for obtaining the polyimide constituting the polyimide film of the present invention include, for example, tetradecahydro-1H, 3H-4,12: 5,11: 6,10-trimethanoanthra [ 2,3-c: 6,7-c ′] difuran-1,3,7,9-tetraone, decahydro-1H, 3H-4,10-ethano-5,9-methanonaphtho [2,3-c: 6 , 7-c ′] difuran-1,3,6,8-tetraone, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, pyromellitic acid, 3,3 ′, 4,4′-. Benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4,4′-oxydiphthalic acid, bis (3,4-dicarbo Ciphenyl) sulfone dianhydride, m-terphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, p-terphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, 9-oxatricyclo [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid, decahydro-1,4: 5,8-dimethanonaphthalene-2,3,6 Derivatives of 7-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic acid, etc. Of the acid dianhydride. Other examples of tetracarboxylic acid components that can be used include 3a, 4,10,10a-tetrahydro-1H, 3H-4,10-methanonaphtho [2,3-c: 6,7-c ′] difuran-1, 3,6,8-tetraone, 3a, 4,6,6a, 9a, 10,12,12a-octahydro-1H, 3H-4,12: 6,10-dimethanoanthra [2,3-c: 6,7- c ′] difuran-1,3,7,9-tetraone, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bis Carboxyphenyldimethylsilane, bisdicarboxyphenoxydiphenyl sulfide, sulfonyldiphthalic acid, isopropylidenediphenoxybisphthalic acid, [1,1′-bi (cyclohexane) −3,3 ′, 4,4′-tetracarboxylic acid, [1,1′-bi (cyclohexane)]-2,3,3 ′, 4′-tetracarboxylic acid, [1,1′-bi (cyclohexane) )]-2,2 ′, 3,3′-tetracarboxylic acid, 4,4′-methylenebis (cyclohexane-1,2-dicarboxylic acid), 4,4 ′-(propane-2,2-diyl) bis ( Cyclohexane-1,2-dicarboxylic acid), 4,4′-oxybis (cyclohexane-1,2-dicarboxylic acid), 4,4′-thiobis (cyclohexane-1,2-dicarboxylic acid), 4,4′-sulfonyl Bis (cyclohexane-1,2-dicarboxylic acid), 4,4 ′-(dimethylsilanediyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4 ′-(tetrafluoropropane-2,2-diyl) Screw (Rohexane-1,2-dicarboxylic acid), octahydropentalene-1,3,4,6-tetracarboxylic acid, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, 6 -(Carboxymethyl) bicyclo [2.2.1] heptane-2,3,5-tricarboxylic acid, bicyclo [2.2.2] oct-5-ene-2,3,7,8-tetracarboxylic acid, Tricyclo [4.2.2.02,5] decane-3,4,7,8-tetracarboxylic acid, tricyclo [4.2.2.02,5] dec-7-ene-3,4,9, Examples thereof include derivatives such as 10-tetracarboxylic acid and acid dianhydrides thereof. These tetracarboxylic acid components (tetracarboxylic acids and the like) may be used alone or in combination of two or more. Here, tetracarboxylic acid components (tetracarboxylic acids and the like) are tetracarboxylic acids and tetracarboxylic acid derivatives such as tetracarboxylic dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides. Represent.

  Examples of the diamine component that can be used to obtain the polyimide constituting the polyimide film of the present invention include p-phenylenediamine, m-phenylenediamine, benzidine, 3,3′-diamino-biphenyl, 2,2′-bis ( Trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, m-tolidine, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, N, N′-bis (4- Aminophenyl) terephthalamide, N, N′-p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4,4′-dicarboxylic acid Bis (4-aminophenyl) ester, p-phenylenebis (p-amino) Benzoate), bis (4-aminophenyl)-[1,1′-biphenyl] -4,4′-dicarboxylate, [1,1′-biphenyl] -4,4′-diylbis (4-aminobenzoate) 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2 -Isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert -Butylcyclohexane, 1,2-diaminocyclohexane, 4,4'-oxydianiline, 3,4 ' Oxydianiline, 3,3′-oxydianiline, bis (4-aminophenyl) sulfide, p-methylenebis (phenylenediamine), 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) Hexafluoropropane, bis (4-aminophenyl) sulfone, 3,3-bis ((aminophenoxy) phenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4- (4-Aminophenoxy) diphenyl) sulfone, bis (4- (3-aminophenoxy) diphenyl) sulfur , Octafluorobenzidine, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-diaminobiphenyl 9,9-bis (4-aminophenyl) fluorene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, and the like. These diamine components may be used individually by 1 type, and can also be used in combination of multiple types.

When schematically showing an example of a method for producing a polyimide film,
(1) A polyimide precursor solution or a polyimide precursor solution composition in which an imidization catalyst, a dehydrating agent, a release aid, inorganic fine particles, etc. are selected and added to a polyimide precursor solution as needed is supported in a film form. A method of obtaining a polyimide film by casting on a body and drying by heating to obtain a self-supporting film, followed by dehydration and desolvation by heating;
(2) A cyclization catalyst and a dehydrating agent are added to the polyimide precursor solution, and further, a polyimide precursor solution composition added by selecting inorganic fine particles as necessary is cast on a support in the form of a film. A method of obtaining a polyimide film by dehydrating and cyclizing and obtaining a self-supporting film by heating and drying as necessary, and then removing the solvent and imidizing it by heating;
(3) When the polyimide is soluble in an organic solvent, a polyimide solution composition added by selecting a mold release aid, inorganic fine particles, etc. is cast on a support in a film form, and partially or by heating and drying A method of obtaining a polyimide film by removing all the solvent and then heating to the maximum heating temperature;
(4) When the polyimide is soluble in an organic solvent, a polyimide solution composition added by selecting a mold release aid, inorganic fine particles and the like is cast on a support in the form of a film, and the solvent is removed by heating. A method of obtaining a polyimide film by heating to the highest heating temperature,
Is mentioned.

  Polyimide precursors are: 1) polyamic acid (also called polyamic acid), 2) polyamic acid ester (at least a part of H of the carboxyl group of the polyamic acid is an alkyl group), 3) polyamic acid silyl ester (of polyamic acid At least a part of H of the carboxyl group can be classified as an alkylsilyl group.

  These polyimide precursors can be produced from a tetracarboxylic acid component and a diamine component that give the aforementioned polyimide structure. For example, the tetracarboxylic acid component (tetracarboxylic dianhydride, etc.) and the diamine component are approximately equimolar in the solvent, preferably the molar ratio of the diamine component to the tetracarboxylic acid component [number of moles of diamine component / tetracarboxylic acid component The number of moles of the compound is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, for example, by reacting while suppressing imidization at a relatively low temperature of 120 ° C. or lower, A solution composition of the polyimide precursor can be obtained.

  As an example of the manufacturing method of a polyimide film, a polyimide precursor composition is cast on a base material, for example, The polyimide precursor composition on this base material is 100-500 degreeC, for example, Preferably 200-500 degreeC, More preferably, a method of imidizing the polyimide precursor while removing the solvent by heat treatment at a temperature of about 250 to 450 ° C. can be mentioned. In addition, a heating profile is not specifically limited, It can select suitably.

  Also, the polyimide precursor composition is cast on a substrate, and preferably dried in a temperature range of 180 ° C. or less to form a polyimide precursor composition film on the substrate, and the resulting polyimide precursor is obtained. The film of the composition is peeled off from the substrate and the end of the film is fixed, or the end of the film is not fixed, for example, 100 to 500 ° C., preferably 200 to 500 ° C., more preferably Can be suitably produced also by heat treatment at a temperature of about 250 to 450 ° C. to imidize the polyimide precursor.

  Further, for example, a polyimide solution composition containing polyimide is cast on a substrate, and is heat-treated at a temperature of, for example, about 80 to 500 ° C., preferably 100 to 500 ° C., more preferably about 150 to 450 ° C. By removing, a polyimide film can be suitably produced. In this case, the heating profile is not particularly limited and can be selected as appropriate.

  Here, as a base material, glass is preferable normally, and the polyimide film / glass base material laminated body which formed the polyimide film on the glass base material is used suitably in order to manufacture the board | substrate for displays etc., for example. .

  The polyimide film / base laminate or the polyimide film obtained as described above can provide a flexible conductive substrate by forming a conductive layer on one side or both sides thereof.

  A flexible conductive substrate can be obtained, for example, by the following method. That is, as a first method, the polyimide film / substrate laminate is not peeled off from the substrate, and the surface of the polyimide film is sputtered, vapor-deposited, printed, etc. by a conductive substance (metal or metal oxide). A conductive layer of conductive layer / polyimide film / base material is produced. Then, if necessary, a transparent and flexible conductive substrate comprising the conductive layer / polyimide film laminate can be obtained by peeling the conductive layer / polyimide film laminate from the substrate.

  As a second method, the polyimide film is peeled off from the substrate of the polyimide film / substrate laminate to obtain a polyimide film, and a conductive substance (metal or metal oxide, conductive organic substance, A conductive layer of conductive carbon, etc.) is formed in the same manner as in the first method, and a transparent and flexible conductive layer comprising a conductive layer / polyimide film laminate or a conductive layer / polyimide film / conductive layer laminate. A conductive substrate can be obtained.

  In the first and second methods, if necessary, before forming a conductive layer on the surface of the polyimide film, a gas barrier layer such as water vapor or oxygen, light adjustment by sputtering, vapor deposition or gel-sol method, etc. An inorganic layer such as a layer may be formed.

  The conductive layer is preferably formed with a circuit by a photolithography method, various printing methods, an inkjet method, or the like.

  The substrate of the present invention thus obtained has a circuit of a conductive layer on the surface of a polyimide film composed of the polyimide of the present invention through a gas barrier layer or an inorganic layer as necessary. This board | substrate can be used suitably as a board | substrate for displays, a touch panel, or a solar cell.

  That is, a transistor (inorganic transistor, organic transistor) is further formed on this substrate by vapor deposition, various printing methods, an ink jet method or the like to manufacture a flexible thin film transistor, and a liquid crystal element, an EL element, a photoelectric transistor for a display device are manufactured. It is suitably used as an element.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. In addition, this invention is not limited to a following example.

  In each of the following examples, the evaluation was performed by the following method.

<Evaluation of polyimide film>
[YI]
Using a UV-visible spectrophotometer / V-650DS (manufactured by JASCO), YI of a polyimide film having a film thickness of 10 μm and a 5 cm square size was measured in accordance with the standard of ASTM E313. The light source was D65 and the viewing angle was 2 °.

[400 nm light transmittance, 308 nm light transmittance, total light transmittance]
Using a UV-visible spectrophotometer / V-650DS (manufactured by JASCO), the light transmittance at a wavelength of 400 nm, the light transmittance at a wavelength of 308 nm, the total light transmittance (wavelength of 380 nm) of a polyimide film having a thickness of 10 μm and a 5 cm square size. Average transmittance at ˜780 nm).

[Haze]
Using a turbidimeter / NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the haze of a polyimide film having a film thickness of 10 μm and a 5 cm square size was measured according to the standard of JIS K7136.

[Weight retention after holding at 400 ° C. for 4 hours]
A polyimide film with a film thickness of 10 μm is cut to a size of about 6 mm square to make a test piece. Using a thermogravimetric measuring device (Q5000IR) manufactured by TA Instruments, several pieces of the cut sample are stacked to give a sample weight of 4 mg, nitrogen. After maintaining at 200 ° C. for 30 minutes in an air stream, the temperature was increased from 200 ° C. to 400 ° C. at a rate of temperature increase of 100 ° C./min and held for 4 hours. The weight retention after 4 hours was determined with the weight when reaching 400 ° C. being 100%.

  The measurement result (TGA chart) of the weight retention when the polyimide film of Example 2 is held at 400 ° C. for 4 hours is shown in FIG. For the polyimide films of Example 1 and Comparative Examples 1 to 3, the weight retention was measured with the same high accuracy.

[Weight retention after holding at 430 ° C. for 1 hour]
A polyimide film with a film thickness of 10 μm is cut to a size of about 6 mm square to make a test piece. Using a thermogravimetric measuring device (Q5000IR) manufactured by TA Instruments, several pieces of the cut sample are stacked to give a sample weight of 4 mg, nitrogen. After maintaining at 200 ° C. for 30 minutes in an air stream, the temperature was increased from 200 ° C. to 430 ° C. at a temperature increase rate of 100 ° C./min and held for 1 hour. The weight retention rate after 1 hour was determined with the weight at 430 ° C. reaching 100%.

[Linear thermal expansion coefficient (CTE)]
A polyimide film having a thickness of 10 μm is cut into a strip having a width of 4 mm to form a test piece, and a TMA / SS6100 (manufactured by SII Nano Technology Co., Ltd.) is used. The distance between chucks is 15 mm, the tensile load is 2 g, the heating rate is 20 ° C. / The temperature was raised to 500 ° C. in minutes. A linear thermal expansion coefficient from 100 ° C. to a predetermined temperature (350 ° C. to 430 ° C.) was determined from the obtained TMA curve.

[Thickness direction retardation of film (R _th )]
A polyimide film having a film thickness of 10 μm and a 5 cm square size was used as a test piece, and a phase difference measurement of the film was performed with an incident angle of 40 ° using a phase difference measuring device (KOBRA-WR) manufactured by Oji Scientific Instruments. From the obtained phase difference, the thickness direction retardation of a film having a thickness of 10 μm was determined.

  Abbreviations, purity, etc. of raw materials used in the following examples are as follows.

[Diamine component]
DABAN: 4,4′-diaminobenzanilide [Purity: 99.90% (GC analysis)]
TFMB: 2,2′-bis (trifluoromethyl) benzidine [Purity: 99.83% (GC analysis)]
4,4′-ODA: 4,4′-oxydianiline [Purity: 99.9% (GC analysis)]
BAPB: 4,4′-bis (4-aminophenoxy) biphenyl PPD: p-phenylenediamine [purity: 99.9% (GC analysis)]
[Tetracarboxylic acid component]
TNDA: Tetradecahydro-1H, 3H-4,12: 5,11: 6,10-trimethanoanthra [2,3-c: 6,7-c ′] difuran-1,3,7,9-tetraone EMDAxx: (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS) -decahydro-1H, 3H-4,10-ethano-5,9-methanonaphtho [2,3-c: 6,7-c ′ Difuran-1,3,6,8-tetraone PMDA-HS: 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride [purity: 99.9% (GC analysis)]
6FDA: 4,4 ′-(2,2-hexafluoroisopropylene) diphthalic dianhydride [Purity: 99.77% (H-NMR analysis)]
s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride [purity: 99.9% (H-NMR analysis)]

[solvent]
NMP: N-methyl-2-pyrrolidone DMAc: N, N-dimethylacetamide

  [Synthesis Example 1 (Synthesis of TNDA)]

Ｍａｃｒｏｍｅｌｅｃｕｌｅｓ，１９９４，２７，１１１７．に記載の方法を参照して、ノルボルナジエンとジシクロペンタジエンとのＤｉｅｌｓ−Ａｌｄｅｒ反応で、１，４，４ａ，５，８，８ａ−ヘキサヒドロ−１，４：５，８−ジメタノナフタレン（ＢＮＤＥ）を合成した。

Macromolecules, 1994, 27, 1117. In the Diels-Alder reaction of norbornadiene with dicyclopentadiene, 1,4,4a, 5,8,8a-hexahydro-1,4: 5,8-dimethananaphthalene (BNDE) Was synthesized.

  In an autoclave having a capacity of 200 mL, 120 g (755.75 mmol) of BNDE and 10 g (75.86 mmol) of dicyclopentadiene were charged. After the system was purged with nitrogen, the reaction was carried out at a temperature of 180 to 185 ° C. for 8 hours. After the reaction, 127.5 g of light brown liquid was obtained. Distillation under reduced pressure was carried out under conditions of a temperature of 87 ° C., a tower top temperature of 73 ° C., and a degree of vacuum of 1.5 kPa to 0.5 kPa, and a fraction containing BNDE was removed. 41.2 g of toluene was added to 29.3 g of the residue, and the temperature was raised to 56 ° C. to complete dissolution. Subsequently, 297 g of methanol was added at the same temperature, followed by cooling to 50 ° C. As a result, a white suspension was obtained in the upper layer, and a two-layer system of yellow oil was obtained in the lower layer. The upper white suspension was removed, concentrated under reduced pressure, and 1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydro-1,4: 5,8: 9,10 as a white solid. -24.03 g of trimethanoanthracene (TNDE) was obtained (purity 94.8 pa% by GC analysis, yield 14.2%).

  In a reaction vessel having a capacity of 1 L, 299 g of methanol, 50 g of chloroform, 200 g (1.48 mol) of copper (II) chloride and 351 mg (1.98 mmol) of palladium chloride were added and stirred. After replacing the atmosphere in the system with carbon monoxide, a solution of 22 g (93.9 mmol) of TNDE dissolved in 92 g of chloroform was added dropwise over 6.5 hours and reacted for 20 hours. After replacing the atmosphere in the system from carbon monoxide to argon, the solvent was distilled off from the reaction mixture, and 506 g of chloroform was added. The same operation was repeated two more times. And insoluble matter was removed by filtration from the brownish green suspension. The obtained solution was washed 3 times with 269 g of a saturated aqueous sodium hydrogen carbonate solution and further washed 3 times with 269 g of purified water, and then 2.2 g of anhydrous magnesium sulfate and 2.2 g of activated carbon were added to the organic layer and stirred. The solution was filtered and then concentrated under reduced pressure to obtain 46.63 g of a brown solid. Next, purification by recrystallization (solvent ratio; toluene: heptane = 1: 1.6) and purification by silica gel chromatography (developing solvent; hexane: ethyl acetate: chloroform = 10: 1: 1) are performed to obtain tetra 18.39 g of methyl tetradecahydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3,6,7-tetracarboxylate (TNME) was obtained (purity of 97 pa% by HPLC analysis, yield) (Rate 41.3%).

TNME 18 g (37.9 mmol), formic acid 53.7 g, and paratoluenesulfonic acid monohydrate 146.6 mg (0.77 mmol) were added to a reaction vessel with a capacity of 200 mL and reacted at a temperature of 98 ° C. to 103 ° C. for 13 hours. . After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 54 g of toluene was added to the concentrate. This operation was repeated 6 times, and formic acid was distilled off almost completely. The obtained suspension was filtered, and the obtained solid was washed with 36 g of toluene and then vacuum-dried at 80 ° C. to obtain 13.28 g of a gray solid. Thereafter, recrystallization with acetic anhydride and further recrystallization with N, N′-dimethylacetamide were performed, and tetradecahydro-1H, 3H-4,12: 5,11: 6,10-trimethanoanthra [2 , 3-c: 6,7-c ′] difuran-1,3,7,9-tetraone (TNDA) (9.87 g, purity 97.4% by ¹ H-NMR analysis, yield 68.6). %).

  [Synthesis Example 2 (Synthesis of EMDAxx)]

３Ｌのオートクレーブに、シス−５−ノルボルネン−エキソ−２，３−ジカルボン酸無水物（ｅｘｏ−ＮＡ）６００ｇ（３．６６ｍｏｌ）、２，６−ジブチルヒドロキシトルエン３００ｍｇを入れた。系内を窒素置換した後、内温−２５℃で１，３−ブタジエン３１９ｇ（５．９１ｍｏｌ）を添加し、反応温度１４０〜１６６℃で３５時間撹拌して、白色固体８６６．２ｇを得た（収率５８％）。そして、得られた白色固体８６６．２ｇをトルエンで再結晶して、白色結晶として（３ａＲ，４Ｒ，９Ｓ，９ａＳ）−３ａ，４，４ａ，５，８，８ａ，９，９ａ−オクタヒドロ−４，９−メタノナフト［２，３−ｃ］フラン−１，３−ジオン（ＯＭＮＡｘｘ）３５９ｇを得た（^１Ｈ−ＮＭＲ分析による純度１００％、収率４５％）。

In a 3 L autoclave, 600 g (3.66 mol) of cis-5-norbornene-exo-2,3-dicarboxylic anhydride (exo-NA) and 300 mg of 2,6-dibutylhydroxytoluene were added. After replacing the system with nitrogen, 319 g (5.91 mol) of 1,3-butadiene was added at an internal temperature of −25 ° C., and the mixture was stirred at a reaction temperature of 140 to 166 ° C. for 35 hours to obtain 866.2 g of a white solid. (Yield 58%). Then, 866.2 g of the obtained white solid was recrystallized with toluene to give (3aR, 4R, 9S, 9aS) -3a, 4, 4a, 5, 8, 8a, 9, 9a-octahydro-4 as white crystals. , 9-methanonaphtho [2,3-c] furan-1,3-dione (OMNAxx) 359 g (100% purity by ¹ H-NMR analysis, 45% yield).

  The physical property values of OMNAxx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.19 (d, J = 12 Hz, 1H), 1.52-1.63 (m, 2H), 1.73-1.82 (m, 2H), 1.89 (d, J = 12 Hz, 1H), 2.27-2.40 (m, 2H), 2.56 (t, J = 1.2 Hz, 2H), 2.98 (d, J = 1.2 Hz, 2H), 5.80-5.92 (m, 2H)
CI-MS (m / z); 219 (M + 1)

120 g (550 mmol) of OMNAxx and 2.2 L of dichloromethane were added to a reaction vessel having a volume of 3 L. While cooling to a temperature of −65 to −60 ° C., a solution of 105.4 g (660 mmol) of bromine dissolved in 200 mL of dichloromethane was added dropwise over 2 hours and reacted for 1 hour. This operation was performed twice. And the reaction liquid for 2 times was collected and concentrated with the evaporator, and the light brown solid was obtained. To the obtained light brown solid, 1.5 L of heptane was added and filtered. The solid collected by filtration was washed with 500 mL of heptane, and then vacuum-dried to obtain (3aR, 4R, 9S, 9aS) -6,7-dibromodecahydro-4,9-methanonaphtho [2,3- c] 313 g of furan-1,3-dione (DBDNAxx) was obtained (purity 100% according to ¹ H-NMR analysis, yield 75%). The filtrate was concentrated under reduced pressure, washed with 500 mL of heptane, and then vacuum-dried to obtain 78.1 g of DBDNAxx as a white solid (100% purity by ¹ H-NMR analysis, 19% yield).

  The physical properties of DBDNAxx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.28 (d, J = 12 Hz, 1H), 1.62 (q, J = 12 Hz, 1H), 1.84-2.24 (m, 5H), 2.59 (s, 2H), 3.03 (dd, J = 7.3 Hz, J = 23 Hz, 2H), 4.32 (ddd, J = 3.3 Hz, J = 5.5 Hz, J = 12 Hz, 1 H), 4.73 (dd, J = 3.0 Hz, J = 7.0 Hz, 1 H)
CI-MS (m / z); 379 (M + 1)

259 g (2.64 mol) of maleic anhydride and 200 g (529 mmol) of DBDNAxx were added to a reaction vessel with a capacity of 2 L, and reacted at a reaction temperature of 190 ° C. for 2 hours. After completion of the reaction, the mixture was cooled to a temperature of 100 ° C. and 900 mL of toluene was added. The mixture was cooled to near room temperature, and the precipitated solid was filtered off. The obtained solid was washed with 900 mL of toluene, and then dried under reduced pressure at 60 ° C. for 3 hours to obtain a light brown solid (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS) -3a, 4 4a, 5,5a, 8a, 9,9a, 10,10a-decahydro-1H, 3H-4,10-ethano-5,9-methanonaphtho [2,3-c: 6,7-c '] difuran- 140.2 g of 1,3,6,8-tetraone (EEMDAxx) was obtained (purity 97.2% by ¹ H-NMR analysis, yield 82%).

In addition, the same operation was performed on 180 g (476 mmol) of DBDNAxx to obtain 139.2 g of EEMDAxx as a light brown solid ( ¹ H-NMR purity 98.9%, yield 92%).

  The physical property values of EEMDAxx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 0.59 (d, J = 12 Hz, 1H), 2.01 (s, 2H), 2.12 (d, J = 12 Hz, 1H), 2 .55 (s, 2H), 2.98 (d, J = 1.4 Hz, 2H), 3.20-3.30 (m, 4H), 6.20 (dd, J = 3.1 Hz, J = 4.4Hz, 2H)
CI-MS (m / z); 314 (M + 1)

  To a reaction vessel having a capacity of 20 L, EEMDAxx 254.9 g (794.8 mmol), 10 L of methanol, 533 g of trimethyl orthoformate, and 63 g of concentrated sulfuric acid were added and stirred at a temperature of 61 to 67 ° C. for 79 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to obtain 513 g of a gray solid. The obtained solid was dissolved in 3256 g of chloroform and added dropwise to 1700 g of a 7 wt% aqueous sodium hydrogen carbonate solution. To the separated organic layer, 31.6 g of anhydrous magnesium sulfate and 26.8 g of activated carbon were added and stirred at room temperature for 1 hour, followed by filtration. The filtrate was washed with 322 g of chloroform and concentrated under reduced pressure to give a gray solid 325. .3 g was obtained. And the obtained gray solid is recrystallized with methanol, and tetramethyl (1R, 4S, 5R, 6R, 7S, 8S, 10S, 11R) -1,4,4a, 5,6,7, 294.9 g of 8,8a-octahydro-1,4-ethano-5,8-methanonaphthalene-6,7,10,11-tetracarboxylate (EEMDxx) was obtained (purity 100% by GC analysis, yield 91). %).

  The physical property values of EEMDxx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.55 (d, J = 11 Hz, 1H), 1.61 (s, 2H), 2.29 (d, J = 11 Hz, 1H), 2 .43 (s, 2H), 2.62 (d, J = 1.9 Hz, 2H), 2.97 (s, 2H), 3.03 (s, 2H), 3.58 (s, 6H), 3.60 (s, 6H), 6.23 (dd, J = 3.2 Hz, J = 4.6 Hz, 2H)
CI-MS (m / z); 407 (M + 1)

  EEMDxx 98.2 g (242 mmol) and 1720 g of methanol were charged into a 3 L autoclave, and 49.1 g of a 10% rhodium-carbon catalyst (manufactured by NE Chemcat, 50% water-containing product) was added. After substituting the system with hydrogen, hydrogen was pressurized to 0.9 MPa and reacted at an internal temperature of 80 ° C. for 4 hours. After completion of the reaction, the precipitated solid was dissolved with 3235 g of N, N′-dimethylformamide, and the reaction product was taken out and filtered through celite to remove the catalyst. This operation was further performed twice on 97.3 g (239 mmol) of EEMDxx. All the filtrates were combined and concentrated under reduced pressure to obtain 289.1 g of a gray solid. The obtained gray solid was recrystallized from 700 g of chloroform and 4373 g of heptane, and tetramethyl (1R, 2R, 3S, 4S, 5R, 6R, 7S, 8S) -decahydro-1,4-ethano-5 was obtained as a fine gray solid. , 8-methanonaphthalene-2,3,6,7-tetracarboxylate (EMDxx) was obtained (purity 99.9 pa% by GC analysis, yield 96%).

  The physical property values of EMDxx were as follows.

¹ H-NMR (CDCl _3, σ (ppm)); 1.52 (d, J = 9.0 Hz, 2H), 1.58 (s, 2H), 1.76 (d, J = 9.0 Hz, 2H), 1.95-2.10 (m, 4H), 2.52 (s, 2H), 2.71 (d, J = 1.6 Hz, 2H), 2.84 (s, 2H), 3 .63 (s, 6H), 3.64 (s, 6H)
CI-MS (m / z); 409 (M + 1)

EMDExx 282.0 g (689.7 mmol), formic acid 1410 g, and paratoluenesulfonic acid monohydrate 3.28 g (17 mmol) were added to a reaction vessel having a capacity of 3 L, and reacted at a temperature of 95 ° C. to 97 ° C. for 19 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 700 mL of toluene was added to the concentrate. This operation was repeated 6 times, and formic acid was distilled off almost completely. The obtained suspension was filtered, and the obtained solid was washed with 490 mL of toluene and then vacuum-dried at 80 ° C. to obtain 219.6 g of a gray solid. Thereafter, recrystallization with acetic anhydride and further recrystallization with N, N′-dimethylformamide were carried out to obtain (3aR, 4R, 5S, 5aS, 8aR, 9R, 10S, 10aS) -decahydro-1H, 3H-4 as a white solid. , 10-ethano-5,9-methanonaphtho [2,3-c: 6,7-c ′] difuran-1,3,6,8-tetraone (EMDAxx) was obtained ( ¹ H-NMR analysis). Purity 99.4%, yield 96%).

Furthermore, 150 g of the obtained EMDAxx was used and purified under sublimation conditions of 250 to 290 ° C./5 Pa to obtain 146 g of EMDAxx as a white solid (100% purity by ¹ H-NMR analysis, recovery rate 97.6%).

  The physical property values of EMDAxx were as follows.

¹ H-NMR (DMSO-d _6, σ (ppm)); 0.98 (d, J = 13 Hz, 1H), 1.15 (d, J = 9.4 Hz, 2H), 1.57 (d, J = 9.4 Hz, 2H), 1.81 (s, 2H), 1.91 (d, J = 13 Hz, 1H), 2.17 (s, 2H), 2.63 (s, 2H), 3 .04 (s, 2H), 3.19 (s, 2H)
CI-MS (m / z); 317 (M + 1)

[Example 1]
In a reaction vessel substituted with nitrogen gas, 0.787 g (3.46 mmol) of DABAN and 0.319 g (0.87 mmol) of BAPB were placed, and NMP was charged, and the total mass of monomers (total of diamine component and carboxylic acid component) Was added in an amount of 22% by mass and stirred at room temperature for 1 hour. To this solution was gradually added 1.607 g (4.36 mmol) of TNDA. The mixture was stirred at room temperature for 48 hours to obtain a uniform and viscous polyimide precursor solution.

  A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 430 ° C. as it is to thermally imidize. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled and dried to obtain a polyimide film having a thickness of 10 μm.

  The results of measuring the properties of this polyimide film are shown in Table 1.

[Example 2]
In a reaction vessel substituted with nitrogen gas, 0.761 g (3.35 mmol) of DABAN and 0.529 g (1.44 mmol) of BAPB were put, and DMAc was charged, and the total mass of monomers (total of diamine component and carboxylic acid component) Was added in an amount of 25% by mass and stirred at room temperature for 1 hour. To this solution, 1.513 g (4.78 mmol) of EMDAxx was gradually added. The mixture was stirred at room temperature for 48 hours to obtain a uniform and viscous polyimide precursor solution.

  A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 430 ° C. as it is to thermally imidize. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled and dried to obtain a polyimide film having a thickness of 10 μm.

  The results of measuring the properties of this polyimide film are shown in Table 1.

[Comparative Example 1]
In a reaction vessel substituted with nitrogen gas, 8.000 g (39.95 mmol) of 4,4′-ODA is put, DMAc is charged, and the total mass of monomers (total of diamine component and carboxylic acid component) is 22 mass%. An amount of 60.117 g was added and stirred at room temperature for 1 hour. PMDA-HS 8.956 g (39.95 mmol) was gradually added to this solution. The mixture was stirred at room temperature for 48 hours to obtain a uniform and viscous polyimide precursor solution.

  A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 400 ° C. as it is, and thermally imidized to be colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled and dried to obtain a polyimide film having a thickness of 10 μm.

  The results of measuring the properties of this polyimide film are shown in Table 1.

[Comparative Example 2]
In a reaction vessel substituted with nitrogen gas, 2,000 g (6.25 mmol) of TFMB was put, and DMAc was added in an amount of 16.904 g in such an amount that the total monomer weight (total of diamine component and carboxylic acid component) was 21% by mass. And stirred at room temperature for 1 hour. To this solution, 1.942 g (4.37 mmol) of 6FDA and 0.551 g (1.87 mmol) of s-BPDA were gradually added. The mixture was stirred at room temperature for 48 hours to obtain a uniform and viscous polyimide precursor solution.

  A polyimide precursor solution filtered through a PTFE membrane filter is applied to a glass substrate, and heated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from room temperature to 400 ° C. as it is, and thermally imidized to be colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled and dried to obtain a polyimide film having a thickness of 10 μm.

  The results of measuring the properties of this polyimide film are shown in Table 1.

[Comparative Example 3]
PDP 26.88 g (0.249 mol) is put in a reaction vessel substituted with nitrogen gas, NMP is added, and 400 g of an amount that makes the total monomer charge (total of diamine component and carboxylic acid component) 20% by mass is added. And stirred at room temperature for 1 hour. To this solution, 73.13 g (0.249 mol) of s-BPDA was gradually added. The mixture was stirred at room temperature for 48 hours to obtain a uniform and viscous polyimide precursor solution.

  A polyimide precursor solution filtered with a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere (oxygen concentration 200 ppm or less) from room temperature to 450 ° C. as it is, and thermally imidized to be colorless. A transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled and dried to obtain a polyimide film having a thickness of 10 μm.

  The results of measuring the properties of this polyimide film are shown in Table 1.

  According to the present invention, it is possible to provide a polyimide film that can be suitably used for various applications such as a substrate for a display, a touch panel, or a solar cell.

Claims (8)

A film containing polyimide,
When the film thickness is measured at 10 μm,
The weight retention when held at 400 ° C. for 4 hours is 99.0% or more,
YI (yellowness) is 10 or less, and
The polyimide film characterized by the linear thermal expansion coefficient between 100-350 degreeC being 55 ppm / K or less.   2. The polyimide film according to claim 1, wherein when the film thickness is measured at 10 μm, the weight retention when held at 430 ° C. for 1 hour is 99.0% or more.   3. The polyimide film according to claim 1, wherein a linear thermal expansion coefficient between 100 and 380 ° C. when measured at a film thickness of 10 μm is 65 ppm / K or less. 4.   The polyimide film according to claim 1, wherein the haze is 2% or less when the film thickness is measured at 10 μm.   5. The polyimide film according to claim 1, wherein a thickness direction retardation (Rth) is 1000 nm or less when the film thickness is measured at 10 μm.   The polyimide film according to any one of claims 1 to 5, wherein the light transmittance at a wavelength of 308 nm when the film thickness is measured at 10 µm is 0.1% or less.   A laminate comprising the polyimide film according to claim 1 formed on a glass substrate.   A substrate for a display, a touch panel, or a solar cell, comprising the polyimide film according to claim 1.

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